CN112968165A - Modified sodium ion positive electrode material, modified sodium ion electrode and preparation method - Google Patents
Modified sodium ion positive electrode material, modified sodium ion electrode and preparation method Download PDFInfo
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Abstract
The invention relates to a modified sodium ion anode material, a modified sodium ion electrode and a preparation method thereof, wherein a sodium source, a metal element and a fluorine source are mixed and sintered to form the modified sodium ion anode material, the molar ratio of an F element is 0.01-50%, the modified sodium ion anode material, a bonding agent and a conductive agent are prepared into slurry, and the slurry is coated on the surface of an aluminum foil to prepare the sodium ion modified electrode. The invention has the beneficial effects that: the modified sodium ion positive electrode material can obviously improve the specific capacity of the material, improve the cycling stability of the material under high multiplying power, and improve the high-temperature cycling performance of the prepared modified sodium ion positive electrode; and the catalyst is prepared only by a high-temperature calcination method, has simple process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of sodium ion batteries, and particularly relates to a modified sodium ion positive electrode material, a modified sodium ion electrode and a preparation method.
Background
Currently, with the continuous development of new energy industry, people pay attention to energy storage density and need to reduce the cost of raw materials urgently; due to the uneven distribution of global lithium resources, the prices of raw materials such as lithium-containing ores and the like are continuously increased in recent years, so that the manufacturing cost of the battery is continuously increased, and the continuous development of new energy industry is seriously hindered; because sodium and lithium are located in the same main group, resources are very rich, and the sodium and the lithium have similar physicochemical properties; when the material is prepared into a corresponding electrode material, the material shows the same properties with the positive electrode material of the lithium ion battery, and becomes one of the first choice for replacing the lithium ion battery.
Although sodium ion batteries have received great attention, they also face a series of problems, due to the larger ionic radius of sodium ions relative to lithium ions, the kinetics during the charge and discharge deintercalation of sodium ions are extremely slow, greatly limiting the ionic transport of the material, resulting in a very low ionic massThe specific capacity of the material is high, and multiple phase transformation problems are often encountered in the charging and discharging process due to the large ionic radius, so that the structure of the material is changed in different degrees, the structural integrity of the material is damaged, and the cycling stability of the sodium ion battery is influenced; ion doping and surface coating are the main solutions to the above problems at present; e.g. Liu, etc. by reaction with Na0.65[Mn0.7Ni0.16Co0.14]O2On the surface of (A) is subjected to NaTi2(PO4)3The capacity retention rate of the material can be obviously improved through coating, but a calcination process of a secondary material is often introduced, so that the manufacturing cost and the complexity of the process of the material are increased; and Sui et al by addition of Na2/3Ni1/3Mn2/3O2Middle doped Mg with supporting function2+And the generation of cracks in the material structure is inhibited, so that the cycle performance of the material is improved. However, the ion doping often causes the specific capacity of the material to be reduced; anionic doping tends to initiate new redox centres relative to cationic doping; but reports on anion modification of that positive electrode material are relatively high; meanwhile, the analysis of the charge compensation mechanism by anion doping is still not well elucidated.
The current anion doping can effectively construct a voltage platform of the material and increase the charge and discharge capacity of the material; meanwhile, the preparation cost of the material is effectively reduced and the economic benefit is increased through simple high-temperature calcination. And the detailed mechanism of the sodium ion anode prepared by anion doping is not reported.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified sodium ion positive electrode material, a modified sodium ion electrode and a preparation method.
The technical scheme adopted by the invention is as follows: a modified sodium ion positive electrode material with molecular formula of NaxMyOzTe，
Wherein M is one or more of Mn, Ni, Co, Ti, Mg, Zn, Cu, Sn, Fe and Al; t is F;
wherein e is more than 0 and less than 2; z is more than 0 and less than 2; y is more than 0 and less than 1; x is more than 0.5 and less than 1; and z + e is 2.
Preferably, the modified sodium ion positive electrode material is an O2 configuration positive electrode material, an O3 configuration positive electrode material, a P2 configuration positive electrode material or a P3 configuration positive electrode material, or a composite layered positive electrode material, a tunnel positive electrode material, a polyanion positive electrode material or a prussian blue and derivative positive electrode material thereof formed by the above configuration positive electrode materials.
The method for preparing the modified sodium ion cathode material comprises the step of mixing and sintering a sodium source, a metal element and a fluorine source to form the modified sodium ion cathode material, wherein the molar ratio of the F element is 0.01-50%.
Preferably, the sodium source, the metal element and the fluorine source are placed in a ball milling tank, dried after ball milling, calcined for 8-20h at 850-.
Preferably, the fluorine source is one or a mixture of PVDF and NaF.
Preferably, the sodium source is one or a mixture of sodium carbonate, sodium hydroxide, sodium nitrate and sodium oxalate.
A modified sodium ion electrode comprising a modified sodium ion positive electrode material.
A method of making a modified sodium ion electrode comprising the steps of:
putting the adhesive into a solvent to prepare an adhesive solution with the mass fraction of 3-10 wt%;
uniformly grinding the modified sodium ion positive electrode material and a conductive agent, adding an adhesive solution, stirring to obtain slurry, and coating the slurry on the surface of an aluminum foil to obtain a modified sodium ion electrode;
wherein the mass ratio of the modified sodium ion positive electrode material to the conductive agent to the adhesive is 7-9: 2-0.5: 1-0.5.
Preferably, the binder is polyvinylidene fluoride or sodium cellulose;
the solvent is N-methyl pyrrolidone or water;
the conductive agent is acetylene black, conductive carbon black or ketjen black.
The invention has the advantages and positive effects that: the modified sodium ion positive electrode material can obviously improve the specific capacity of the material, improve the cycling stability of the material under high multiplying power, and improve the high-temperature cycling performance of the prepared modified sodium ion positive electrode; and the catalyst is prepared only by a high-temperature calcination method, has simple process and low cost, and is suitable for industrial production.
Drawings
FIG. 1 is a first charge and discharge curve of example 3 of the present invention and comparative example 3;
FIG. 2 is a graph of the cycle number at 2C magnification for example 3 of the present invention and comparative example 1.
Detailed Description
According to the invention, the sodium ion anode material is modified by using different fluorine sources, so that bulk phase doping construction and analysis are realized for the first time, the modified sodium ion anode material can improve the specific surface area and the conductivity of the material, the discharge specific capacity of the material is improved, the Taylor effect of the material is inhibited, and the charge and discharge performance under high temperature and high multiplying power is improved.
The molecular formula of the modified sodium ion anode material is NaxMyOzTeWherein M is one or more of Mn, Ni, Co, Ti, Mg, Zn, Cu, Sn, Fe and Al; t is F; wherein e is more than 0 and less than 2; z is more than 0 and less than 2; y is more than 0 and less than 1; x is more than 0.5 and less than 1; and z + e is 2. The modified sodium ion anode material is an O2 configuration anode material, an O3 configuration anode material, a P2 configuration anode material or a P3 configuration anode material, or a composite layered anode material, a tunnel type anode material, a polyanion type anode material or a Prussian blue and derivative anode material formed by the above configuration anode materials. The preparation method of the modified sodium ion cathode material comprises the following steps: and mixing and sintering a sodium source, a metal element and a fluorine source to form the modified sodium ion positive electrode material, wherein the molar ratio of the F element is 0.01-50%. Specifically, the sodium source, the metal element and the fluorine source are placed in a ball milling tank, dried after ball milling, calcined for 8-20h at 850-1000 ℃, and naturally cooled to room temperature to obtain the modified sodium ion cathode material. Wherein, the fluorine source is one or a mixture of PVDF and NaF; the sodium source is one or a mixture of sodium carbonate, sodium hydroxide, sodium nitrate and sodium oxalate.
The modified sodium ion electrode made of the modified sodium ion anode material also has better high-temperature cycle performance. A method of making a modified sodium ion electrode comprising the steps of:
the method comprises the following steps: weighing a sodium source, a metal element and a fluorine source, putting the sodium source, the metal element and the fluorine source into a ball milling tank to enable the molar ratio of the F element to be 0.01-50%, carrying out ball milling, then drying at high temperature, calcining at the temperature of 850-;
putting the adhesive into a solvent to prepare an adhesive solution with the mass fraction of 3-10 wt%;
uniformly grinding the modified sodium ion positive electrode material and a conductive agent, adding a prepared binder solution, continuously stirring to obtain corresponding slurry, and coating the slurry on the surface of an aluminum foil to obtain a modified sodium ion electrode; wherein the mass ratio of the modified sodium ion positive electrode material to the conductive agent to the adhesive is 7-9: 2-0.5: 1-0.5.
Wherein the sodium source is one or a mixture of sodium carbonate, sodium hydroxide, sodium nitrate and sodium oxalate; the binder is polyvinylidene fluoride or sodium cellulose; the solvent is N-methyl pyrrolidone or water; the conductive agent is acetylene black, conductive carbon black or Ketjen black.
The following embodiments are provided to specifically describe the scheme of the present invention, wherein the experimental methods without specific description of the operation steps are all performed according to the corresponding commercial specifications, and the instruments, reagents and consumables used in the embodiments can be purchased from commercial companies without specific description.
Example 1
The preparation method of the modified sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、NiO、MnCO3Uniformly mixing the materials according to the corresponding molar stoichiometric ratio of 1.03:0.5:0.5, adding PVDF to make the F element proportion of 0.01, adding a proper amount of NMP to uniformly mix, drying, heating to 850 ℃ for 20h through 10 DEG/min, maintaining calcination, naturally cooling to room temperature, grinding to obtain a corresponding product, namely the modified sodium ion anode material, and placing the modified sodium ion anode material into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 5%;
c. sequentially adding acetylene black and a modified sodium ion positive electrode material, stirring and dispersing to form slurry, and coating the slurry on one surface of an aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the modified sodium ion positive electrode material to the acetylene black to the polyvinylidene fluoride is 8: 1: 1.
example 2
The preparation method of the modified sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、NiO、MnCO3、TiO2Uniformly mixing the materials according to the corresponding molar stoichiometric ratio of 1.03:0.45:0.5:0.05, adding NaF to enable the content of the F element to be 0.03, adding a proper amount of NMP to uniformly mix the materials, drying the materials, heating the materials to 900 ℃ through 5 DEG/min, maintaining the calcination for 20 hours, naturally cooling the materials to room temperature, grinding the materials to obtain the corresponding product, namely the modified sodium ion anode material, and putting the modified sodium ion anode material into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 6%;
c. sequentially adding acetylene black and a modified sodium ion positive electrode material, stirring and dispersing to form slurry, and coating the slurry on one surface of an aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the modified sodium ion positive electrode material to the acetylene black to the polyvinylidene fluoride is 7: 2: 1.
example 3
The preparation method of the modified sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、NiO、MnCO3Uniformly mixing the raw materials according to the corresponding molar stoichiometric ratio of 2:1:3, adding NaF until the content of the F element is 0.05, adding appropriate amount of ethanol, uniformly mixing, drying, heating to 920 ℃ for 12h at 5 ℃/min, and naturally coolingCooling to room temperature, grinding to obtain a corresponding product, namely the modified sodium ion anode material, and placing the modified sodium ion anode material into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 6%;
c. sequentially adding acetylene black and a modified sodium ion positive electrode material, stirring and dispersing to form slurry, and coating the slurry on one surface of an aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the modified sodium ion positive electrode material to the acetylene black to the polyvinylidene fluoride is 8: 1: 1.
example 4
The preparation method of the modified sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、MnCO3、Al2O3Uniformly mixing the materials according to the corresponding molar stoichiometric ratio of 0.44:0.85:0.15, adding PVDF to enable the F element proportion to be 0.2, adding a proper amount of NMP to uniformly mix, drying, heating to 950 ℃ for 10 hours through 5 DEG/min, calcining, naturally cooling to room temperature, grinding to obtain a corresponding product, namely the modified sodium ion anode material, and putting the modified sodium ion anode material into a glove box filled with argon for later use;
b. adding a binder (a mixture of sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 1: 1) into water, and stirring to dissolve the binder to obtain a binder solution with a mass concentration of 6%;
c. sequentially adding ketjen black and the modified sodium ion positive electrode material, stirring and dispersing to form slurry, and coating the slurry on one surface of the aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the modified sodium ion positive electrode material to the Ketjen black to the polyvinylidene fluoride is 7: 2: 1.
example 5
The preparation method of the modified sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、V2O5、NH4H2PO4To make their respective molar stoichiometric ratiosUniformly mixing according to the ratio of 3.03:2:3, then adding NaF to enable the proportion of the F element to be 0.9, adding a proper amount of NMP to enable the NaF element to be uniformly mixed, drying, heating to 800 ℃ through 8 DEG/min, maintaining calcination for 16 hours, then naturally cooling to room temperature, grinding to obtain a corresponding product, namely the modified sodium ion anode material, and placing the modified sodium ion anode material into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 6%;
c. sequentially adding acetylene black and a modified sodium ion positive electrode material, stirring and dispersing to form slurry, and coating the slurry on one surface of an aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the modified sodium ion positive electrode material to the acetylene black to the polyvinylidene fluoride is 7: 2: 1.
example 6: preparation of sodium ion battery
Preparing a counter electrode: taking the sodium block out of the kerosene, removing oxides on the surface, and preparing a counter electrode plate through rolling and cutting;
preparing a sodium ion electrolyte: according to the volume ratio of 95:5, cell-grade propylene carbonate and fluoroethylene carbonate are uniformly mixed, and 1M NaClO with final concentration is added4；
The modified sodium ion positive electrode prepared in examples 1 to 5, a counter electrode and a sodium ion electrolyte were assembled into a sodium ion battery in a glove box.
Comparative example 1
The preparation method of the sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、NiO、MnCO3Heating to 850 ℃ for calcination for 20 hours after the corresponding molar stoichiometric ratio is 1.03:0.5:0.5, then heating to 850 ℃ through 10 DEG/min, naturally cooling to room temperature, grinding to obtain a corresponding product, namely a sodium ion anode, and placing the sodium ion anode into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 5%;
c. sequentially adding acetylene black and a sodium ion anode, stirring and dispersing to form slurry, and coating the slurry on one surface of the aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the sodium ion positive electrode to the acetylene black to the polyvinylidene fluoride is 8: 1: 1.
comparative example 2
The preparation method of the sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、NiO、MnCO3、TiO2Uniformly mixing the materials according to the corresponding molar stoichiometric ratio of 1.03:0.45:0.5:0.05, heating to 900 ℃ for calcination for 20 hours at the temperature of 5 DEG/min, naturally cooling to room temperature, grinding to obtain a corresponding product, namely a sodium ion anode, and putting the sodium ion anode into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 6%;
c. sequentially adding acetylene black and a sodium ion anode, stirring and dispersing to form slurry, and coating the slurry on one surface of the aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the sodium ion positive electrode to the acetylene black to the polyvinylidene fluoride is 7: 2: 1.
comparative example 3
The preparation method of the sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、NiO、MnCO3Uniformly mixing the materials according to the corresponding molar stoichiometric ratio of 2:1:3, adding a proper amount of ethanol, uniformly mixing, drying, heating to 920 ℃ for 12h through 5 ℃/min, naturally cooling to room temperature, grinding to obtain a corresponding product, namely a sodium ion anode, and placing the sodium ion anode into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 6%;
c. sequentially adding acetylene black and a sodium ion anode, stirring and dispersing to form slurry, and coating the slurry on one surface of the aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the sodium ion positive electrode to the acetylene black to the polyvinylidene fluoride is 8: 1: 1.
comparative example 4
The preparation method of the modified sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、MnCO3、Al2O3Uniformly mixing the components according to the corresponding molar stoichiometric ratio of 0.44:0.85:0.15, heating to 950 ℃ for calcination for 10 hours at 5 ℃/min, naturally cooling to room temperature, grinding to obtain a corresponding product, namely a sodium ion anode, and placing the sodium ion anode into a glove box filled with argon for later use;
b. adding a binder (a mixture of sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 1: 1) into water, and stirring to dissolve the binder to obtain a binder solution with a mass concentration of 6%;
c. sequentially adding Ketjen black and a sodium ion anode, stirring and dispersing to form slurry, and coating the slurry on one surface of an aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the sodium ion positive electrode to the Ketjen black to the polyvinylidene fluoride is 7: 2: 1.
comparative example 5
The preparation method of the sodium ion positive electrode comprises the following steps:
a. weighing Na2CO3、V2O5、NH4H2PO4Uniformly mixing the materials according to the corresponding molar stoichiometric ratio of 3.03:2:3, heating to 800 ℃ for 8 DEG/min, maintaining the calcination for 16 hours, naturally cooling to room temperature, grinding to obtain a corresponding product, namely a sodium ion anode, and putting the sodium ion anode into a glove box filled with argon for later use;
b. adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring to dissolve the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution with the mass concentration of 6%;
c. sequentially adding acetylene black and a sodium ion anode, stirring and dispersing to form slurry, and coating the slurry on one surface of the aluminum foil; obtaining a modified sodium ion anode; the mass ratio of the sodium ion positive electrode to the acetylene black to the polyvinylidene fluoride is 7: 2: 1.
the sodium ion positive electrodes prepared in comparative examples 1 to 5 above were assembled into lithium batteries in a glove box with a counter electrode and a sodium ion electrolyte according to the method of example 6.
TABLE 1 shows the electrochemical properties of the modified sodium ion positive electrodes prepared in examples 1-5 and comparative examples 1-5
The data in table 1 show that the initial capacity and capacity retention rate of the positive electrode prepared from the sodium ion positive electrode material modified by the fluorine source are superior to those of an unmodified positive electrode under the same conditions, and the high-pressure rate performance of the material can be obviously improved by modifying the sodium ion positive electrode material by the fluorine source. Example 3 and comparative example 3 were selected for further comparison, as shown in fig. 1 and 2, fig. 1 is a first charge and discharge curve of example 3 and comparative example 3, and it can be seen from the first charge and discharge curve that the capacity of example 3 is higher than that of comparative example 3. To further study the comparison of the cycling performance of the two materials of example 3 and comparative example 3, the materials were subjected to charge-discharge cycling at 2C rate, as shown in FIG. 2, and after cycling at 2C rate, 400 times, the specific discharge capacity of example 3 still reached 95.4mAh g-1Much higher than 84.9mAh g in comparative example 3-1. By contrast, the doped material, in both capacity and cycle performance, is greatly improved compared with the undoped material, which fully shows the superiority and practicability of the modification method.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A modified sodium ion anode material, which is prepared from sodium ion,the method is characterized in that: molecular formula is NaxMyOzTe，
Wherein M is one or more of Mn, Ni, Co, Ti, Mg, Zn, Cu, Sn, Fe and Al; t is F;
wherein e is more than 0 and less than 2; z is more than 0 and less than 2; y is more than 0 and less than 1; x is more than 0.5 and less than 1; and z + e is 2.
2. The modified sodium ion positive electrode material according to claim 1, characterized in that: the modified sodium ion anode material is an O2 configuration anode material, an O3 configuration anode material, a P2 configuration anode material or a P3 configuration anode material, or a composite layered anode material, a tunnel type anode material, a polyanion type anode material or a Prussian blue and derivative anode material formed by the above configuration anode materials.
3. A method of preparing the modified sodium ion positive electrode material of claim 1, characterized in that: and mixing and sintering a sodium source, a metal element and a fluorine source to form the modified sodium ion positive electrode material, wherein the molar ratio of the F element is 0.01-50%.
4. The method for preparing a modified sodium ion positive electrode material according to claim 3, characterized in that: and (3) putting the sodium source, the metal element and the fluorine source into a ball milling tank, drying after ball milling, calcining for 8-20h at 850-1000 ℃, and naturally cooling to room temperature to obtain the modified sodium ion anode material.
5. The method for preparing a modified sodium ion positive electrode material according to claim 4, characterized in that: the fluorine source is one or a mixture of PVDF and NaF.
6. The method for preparing a modified sodium ion positive electrode material according to claim 4, characterized in that: the sodium source is one or a mixture of sodium carbonate, sodium hydroxide, sodium nitrate and sodium oxalate.
7. A modified sodium ion electrode comprising the modified sodium ion positive electrode material of claim 1 or 2.
8. A method of making the modified sodium ion electrode of claim 7, wherein: the method comprises the following steps:
putting the adhesive into a solvent to prepare an adhesive solution with the mass fraction of 3-10 wt%;
uniformly grinding the modified sodium ion positive electrode material and a conductive agent, adding an adhesive solution, stirring to obtain slurry, and coating the slurry on the surface of an aluminum foil to obtain a modified sodium ion electrode;
wherein the mass ratio of the modified sodium ion positive electrode material to the conductive agent to the adhesive is 7-9: 2-0.5: 1-0.5.
9. The method for preparing a modified sodium ion electrode according to claim 8, wherein: the binder is polyvinylidene fluoride or sodium cellulose;
the solvent is N-methyl pyrrolidone or water;
the conductive agent is acetylene black, conductive carbon black or ketjen black.
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